New cadmium and rare earth metal tungstates with the scheelite type structure

New cadmium and rare earth metal tungstates with the formula Cd0.25RE0.50 0.25WO4 （RE=Nd, Sin, Eu, Gd, D-statistical distrib- uted vacancies in cation sublattice） were synthesized by the solid-state reaction between CdWO4 and corresponding RE2W209. The obtained phases crystallize in the scheelite type structure. The Cd0.25RE0.5 0.25WO4 compounds were characterized by X-ray diffractometer （XRD）, （DTA-TG）, infrared （IR） and EPR methods.

Synthesis of Polymer-Bonded Quaternary Ammonium Type Metal Porphyrins

The reaction of pyrrole with 4-hydroxybenzaldehyde and 4-pyridinecarboxaldehyde afforded new porphyrin ligand 1. Treatment of 1 with copper( II ) acetate, cobalt ( II ) acetate gave complexes 2-3 respectively. 2 and 3 reacted with Merrifield's peptide resin produced 4 and 5. Complexes 4 and 5 reacted with methyl iodide respectively gave 6-7. The new compounds 1-7 have been identified by H-1 NMR, IR, MS and UV-visible spectra, elemental analysis and AES.

BASIC REGULARITY OF PETROGENESIS AND METALLOGENESIS OF NANLING CRUST-DERIVED TYPE GRANITOIDS

In the light of analysis of the internal relations among the source strata for magmatism, thegranitic magmas and the endogenic metallizations, the basic regularity of petrogenesis and metallo-genesis of Nanling crust-derived type granitoids can be generalized as follows: (1) Two suites ofsource strata for Magmatism-the Pre-Sinian and the Lower Sinianl here the unity of the old foldbasement, the source strata for magmatism and the source strata for metallization are particularlyhighlighted. (2) Multi-stage melting of source strata for magmatism resulting in the formation ofmajor ore-related granites of three different stages (the Late Jinningean stage, the Late Caledonianstage, and the Late Indosinian-Late Yanshanian stage) under the control of tw0 tectonic units(geosyncline and diwa). (3) Three endogenic meta1logenic epoches accompanying the three stagesof ore-related granitic magmatism. (4) One major metallogenic epoch characterized by concentrat-ed commercial metallizations in large scale related to the Yanshanian crust-derived type granites.Tectonically,this major metallogenic epoch is exactly consistent with the stage of violent diwa ac-tivity. This is by no means fortuitous, but is the unavoidable result of the development and evolu-tion of the objective geologic history.

STUDIES ON THE PROPERTIES OF SCHIFF BASE TYPE ARYLMERCURY COMPOUNDS Ⅲ TRANSMETALLATION REACTION OF SCHIFF BASE TYPE ARYLMERCURY COMPOUNDS WITH METALLIC TIN

The transmetallation reaction of 4 Schiff base type arylmercury compounds with metallic tin has been carried out in refluxing xylene.It was found that the reaction proceeds in the same manner as that of chloro[2-(phenylazo)phenyl]mercury(Ⅱ) to give dichlorobisaryltin(Ⅳ).The ~1H NMR spectra of the products provide evidence for the presence of N→Sn intramolecular coordination.The formation of dichlorobisaryltin(Ⅳ)as a unique product probably arises from the N→Sn intramolecular coordination which results in the increasing of the stability of the molecule.

Removal of Anionic Metal Ions from Wastewater by Hydroxide-type Adsorbents

Generally speaking,anionic metal concentrations in wastewater from industries and mineral processing plants are well above the allowed limits for effluent set by the Ministry of Environment of Japan. Nowadays,the removal of anionic ions has been considered difficult and development of new process is desperately needed. In this paper,we report the development of three hydroxide-type adsorbents,illustrating their adsorption efficiency in removing As,Se,Mo and Sb ions from aqueous solutions. The main finding of this work was that the adsorption behavior was influenced very much by both the pH and the adsorbent concentration. Nevertheless,the newly developed hydroxide-type adsorbents were very effective in reducing the concentration of those anionic ions.

Effects of gate-buffer combined with a p-type spacer structure on silicon carbide metal semiconductor field-effect transistors

An improved structure of silicon carbide metal-semiconductor field-effect transistors （MESFET） is proposed for high power microwave applications. Numerical models for the physical and electrical mechanisms of the device are presented, and the static and dynamic electrical performances are analysed. By comparison with the conventional structure, the proposed structure exhibits a superior frequency response while possessing better DC characteristics. A p-type spacer layer, inserted between the oxide and the channel, is shown to suppress the surface trap effect and improve the distribution of the electric field at the gate edge. Meanwhile, a lightly doped n-type buffer layer under the gate reduces depletion in the channel, resulting in an increase in the output current and a reduction in the gate-capacitance. The structural parameter dependences of the device performance are discussed, and an optimized design is obtained. The results show that the maximum saturation current density of 325 mA/mm is yielded, compared with 182 mA/mm for conventional MESFETs under the condition that the breakdown voltage of the proposed MESFET is larger than that of the conventional MESFET, leading to an increase of 79% in the output power density. In addition, improvements of 27% cut-off frequency and 28% maximum oscillation frequency are achieved compared with a conventional MESFET, respectively.

A New Sandwiched-type Polyoxotungstate Containing {Cd_4} Transition-metal Cluster:Synthesis,Structure and Luminescent Property

A new sandwiched polyoxometalate [HK11Cd4Cl2（PW9034）2]·18H2O （1）, incor- porating a unique hybrid tetranuclear cadmium cluster （abbreviated to {Cd4}） with two trivacant polyanions [B-α-PW9O34]9-, has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, UV-vis, and single-crystal X-ray diffraction analysis. Crystal data for 1： monoclinic, space group C2/c, a = 19.2997（4）, b = 13.8014（3）, c = 31.9819（8） A, β = 102.764（2）°, V= 8308.3（3） A3, Z = 4, P2O86Cl2K11Cd4W18H37, Mr = 5735.13, Dc = 4.584 mg-mm-3, F（000） = 10084, μ = 26.579 mm-1, the final R = 0.0378 and wR = 0.0989 for 6558 observed reflections （I〉 2σ（I））. X-ray crystallographic study shows that the molecular structure of 1 contains four cadmium atoms. Two CdO6 distorted octahedra and two CdOsC1 distorted octahedra combine with each other in turn via edge-sharing, resulting in a regular rhomb-like cluster sandwiched between two {B-a-PW9034} units. Further, the sandwich-type polyoxoanions were connected by K＋ ions to form a complicated 3-D open-framework through connecting with each terminal O atom of the [Cd4C12（PW9O34）2]12- polyoxoanions. In addition, compound 1 exhibits photoluminescence property at room temperature and the band gap can be assessed at 3.25 eV.

Heavy metal(loid) pollution in mine wastes of a Carlin-type gold mine in southwestern Guizhou, China and its environmental impacts

Mercury pollution resulting from artisanal gold mining is a serious environmental problem in many developing countries. In this study, we analyzed heavy metal(loid) contamination in mine wastes from a Carlin-type gold mine in southwestern Guizhou, China. Highly elevated levels of As, Hg, Tl, Sb, and Cd—up to 5844, 28,29, 581 and 3.0 mg/kg, respectively—were observed in the mine wastes, but no significant accumulation of Cr, Ni, Cu,Zn, and Pb was found. The smelting process of gold ores had significant impacts on the enrichment of As, Tl, and Hg in the mine wastes. Due to the significant metal(loid)pollution in this gold mine, the ecological risks are classified as ‘‘very high.'' Hg and As are the major pollutants with a relative contribution of 55.9 % and 24.2 % to the risk index, respectively. Phytoremediation could be used to reduce heavy metal contamination and recycle the gold simultaneously. Hg–As–Tl pollution should be considered in gold extraction at Carlin-type gold mines.

Analysis and Assessment on the Heavy Metals in a Severely Degraded Subtropical Red Soil Region

5 different forests of Pinus massoniana, Schima superba, Liquidambar formosana, P. massoniana × S. superba, P. massoniana × L. formosana as the research object were set up to study the Cr, Cu and Zn content of degraded red soil region in subtropics. The soil heavy metal pollution degree was evaluated by national environmental quality standard (II class). The results showed that three soil metals of P. massoniana × S. superba were the highest, and the soil metals enrichment ability was strong. The order of single factor pollution index of metal elements was Cu (1.38) > Cr (0.81) > Zn (0.42), and moderately pollution, pollution warning and no pollution, respectively. There was no significant correlation between three soil heavy metals and soil total carbon (TC), total nitrogen (TN) and total phosphorus (TP). These results suggested that the accumulation of heavy metal elements was not derived from the parent material of soil. There was a significant positive correlation between the three metal elements which indicated that the sources of the three elements were similar. The structural equation model showed that the direct and indirect effects among the influencing factors ultimately affected the activity of heavy metals by cascade effects.

各种金属参与的水相Barbier-Type反应

详细地概括了各种金属和金属盐参与的水相Barbier Type反应 ,对反应机理以及反应的化学、区域和立体选择性进行了系统的总结 ,此外 ,还对水相Barbier Type反应在有机合成中的应用作了初步的介绍 .

微紫青霉菌(Penicillium janthinellum)P-type ATPase及金属硫蛋白相关基因的克隆

本研究以高抗多种重金属盐的微紫青霉菌(Penicillium janthinellum)菌株GXCR为材料构建基因组fosmid文库。其插入片段集中在36～50kb,含13348个克隆,重组率为100%,大约覆盖了GXCR基因组的14.83倍。基于序列特异性和简并引物,利用PCR扩增分析了与酿酒酵母(Saccharomyces cerevisiae)重金属盐抗性相关的CRS5和CUP2基因;基于兼并引物和序列特异性引物,利用PCR扩增分析了GXCR的P-type ATPase基因。通过菌落原位杂交和Southern blot鉴定了一个含铜转运P-type ATPase基因的阳性fosmid克隆,经亚克隆测序分析表明该基因与棒曲霉(Aspergillus clavatus菌株)NRRL1的P-type copper ATPase相似性达97%。没有筛选到与CRS5和CUP2基因同源的克隆,说明GXCR中可能不存在与酿酒酵母CUP2和CRS5高度同源的MT基因,同时也暗示酵母与丝状真菌的重金属盐的抗性机制有本质上的差异或者独特性。

Evolution of Pore Size Distribution and Mean Pore Size in Lotus-type Porous Magnesium Fabricated with Gasar Process

The effect of gas pressures on the mean pore size, the porosity and the pore size distribution of lotus-type porous magnesium fabricated with Gasar process were investigated. The theoretical analysis and the experimental results all indicate that there exists an optimal ratio of the partial pressures of hydrogen PH2 to argon PAr for producing lotus-type structures with narrower pore size distribution and smaller pore size. The effect of solidification mode on the pore size distribution and pore size was also discussed.

SYNTHESIS, CHARACTERIZATION, METAL-UPTAKE BEHAVIOR OF BIS(BENZIMIDAZOLE) RESIN SUPPORTED ON EPOXIDE POLYMER

The new chelate resins, abbreviated as PNBMZs and PBBMZs based on epoxide polymer, were synthesized by polycondensation of N,N-diglycidyl-4-glycidyloxyaniline or 1,4-bis（2,3-epoxypropyl）benzene with the primary amine group of 1,3-bis（benzimidazol-2yl）propylamine （BBPAH）. The ion exchangers contain 2.71-3.23 mmol of the ligand contents per gram of the resin. Batch extraction capacities were determined for the metal chloride salts in buffer solutions in the pH range from -1 to 6.0. The chelate resins were very selective for Cu^2＋, Zn^2＋, Cd^2＋ in the presence of other divalent transition metal ions. The maximum uptake capacities of PNBMZ （synthetic molar ratio = 1：1.5） under non-competitive condition were found to be 0.94 mmol/g for Cu^2＋ at pH = 2, 1.3 mmol/g for Cd^2＋ at pH = 1 and 1.75 mmol/g for Zn^2＋ at pH = -1 respectively. While in the case of PBBMZ, it was 1.39 mmol/g for Cd〉 at pH = 1. The metal-uptake behaviors for both of them showed strong pH dependence, and their extraction capacities increase with decreasing pH. The uptake of Cu^2＋ by the resin PNBMZs at pH = 1 was found to be rather fast with t1/2 = 18 min. Metal-uptake experiments under competitive conditions also confirm that the chelate resins have a high selectivity for Cu^2＋, Zn^2＋, Cd^2＋ and the contrary pH dependence.

First-principles Study of Divalent ⅡA and Transition ⅡB Metals Doping into Cu_2O

Divalent IIA metals such as Be, Mg, Ca, Sr, Ba and transition IIB metals such as Zn, Cd were investigated as possible n-type dopants into the Cu2 O theoretically by using the first-principles calculations based on density functional theory. By systematical analyses of the lattice parameters, the bond length, the electronic structure, the local density of states and the defect formation energy for various doping systems, it is revealed that Ca, Sr, Ba and Be are more suited for n-type doping into Cu2O as shallow donors, compared to Mg which introduces a relatively deep donor level in Cu2O. Meanwhile, Zn and Cd can hardly be doped into Cu2O due to the positive formation energy of relevant defects.

Petrogenesis and Mineralization of Two-Stage A-Type Granites in Jiuyishan,South China:Constraints from Whole-rock Geochemistry, Mineral Composition and Zircon U-Pb-Hf Isotopes

The Jiuyishan complex massif,located in the northern section of the Nanling region,is a combination of five plutons,namely,the Xuehuading,Jinjiling,Pangxiemu,Shaziling and Xishan plutons.Whole-rock geochemistry,Imineral electron microprobe analysis,zircon U-Pb dating and Hf isotope analysis were carried out for the Jinjiling and Pangxiemu plutons.The zircon U-Pb dating yields weighted mean ages of 152.9±0.9 Ma for the Jinjiling pluton and 151.7±1.5 Ma for the Pangxiemu pluton,with a narrow gap between them.The Jinjiling and Pangxiemu plutons both have geochemical characteristics of high SiO2,Al2 O3,Na2 O,K2 O and low TiO2,MgO,CaO,P2 O5 contents,with intense depletions in Sr,Ba,Ti,Eu and enrichments in Ga,FeoOT and HFSE,and these characteristics reflect an A-type affinity.From the Jinjiling to the Pangxiemu plutons,the mineral composition of mica changes from lepidomelane to zinnwaldite,with increases in F,Li2 O and Rb2 O contents.The mineral composition of zircon changes from low Zr/Hf to high Zr/Hf,with increasing HfO2,P2 O5 and UO2+ThO2+Y2 O3 contents.The mineral compositions of feldspar indicate that the Pangxiemu pluton contains more alkali feldspar than the Jinjiling pluton.The whole-rock geochemistry and mineral compositions reveal a higher degree of differentiation for the Pangxiemu pluton.The nearly uniformεHf(t)indicates the same source region for the two plutons:both were derived from partial melting of the lower crust,with small contributions of mantle materials.In addition,higher F,lower Nb/Ta and Zr/Hf ratios in the Pangxiemu Pluton suggest a closer relationship with the rare metal mineralization than for the Jinjiling pluton.

新疆阿尔金西段瓦石峡南锂铍稀有金属矿成矿背景与勘查进展

锂、铍等稀有金属矿产是重要的战略矿产资源。近年来,在阿尔金地区发现了多处稀有金属伟晶岩型矿床,已成为我国一处新的稀有金属成矿带,但调查研究水平总体较低。通过对阿尔金造山带的成矿动力背景的讨论,得出阿尔金造山带的稀有金属成矿作用涵盖了多个不同的造山运动构造演化阶段,证明该区域具备良好的稀有金属成矿条件,并具有巨大的找矿潜力。通过对位于阿尔金西段的瓦石峡南锂铍稀有金属矿进行勘查评价,发现其具有大型远景:瓦石峡南锂铍稀有金属矿体主要赋存于绿片岩相-角闪岩相变质岩系中的伟晶岩脉中,矿床类型为花岗伟晶岩型稀有金属矿床;已有勘查成果显示此矿床目前推断的稀有金属资源量达到中型以上矿床规模,并且随着勘查工作的进行,在深部及外围还有极大增储空间。研究成果对在阿尔金造山带内寻找同类型矿床具有借鉴意义。

Synthesis, Characterization and Metal Ion Adsorption Studies on Novel Aromatic Poly(Azomethine Amide)s Containing Thiourea Groups

A series of novel ladder-type poly(azomethine amide)s (PAMs) were prepared from new azomethine containing carboxylic acid monomer (TCA) with simple aromatic diamines and aromatic diamines with thiourea groups (TDAs) by means of phosphorylation polycondensation reaction. Molecular weights of the polyamides were evaluated viscometrically, and the inherent viscosities were in the range of 0.31 - 0.58 g/dl. These ladder-type polymers were not freely soluble in common organic solvents. Structure of monomers and polymers were confirmed using FT-IR, 1H-NMR and 13C-NMR spectroscopic analysis. Removal of Cu2+ and Cd2+ from aqueous solutions by adsorption onto the polyamides was investigated. The effect of pH, initial metal ion concentrations and contact time were studied in batch experiments. The polyamides were found to be highly effective adsorbents for the removal of Cu2+ and Cd2+ metal ions from aqueous solutions. In a mixture of metal ions, the selectivity order was found to be Pb(II) > Cu(II) > Cr(IV) > Cd(II).

Isotopes and Geochronology of the Meixian-type Pb-Zn-(Ag)Deposits,Central Fujian Rift,South China:Implications for Geological Events

Central Fujian Rift is another new and important volcanogenic massive sulfide Pb-Zn polymetallic metallogenetic belt. In order to find out the material genesis and mineralization period of Meixian-type Pb-Zn-Ag deposits, S and Pb isotope analysis and isotope geochronology of ores and wall rocks for five major deposits are discussed. It is concluded that the composition of sulfur isotope from sulfide ore vary slightly in different deposits and the mean value is close to zero with the 834S ranging from -3.5‰ to ＋5.6‰ averaging at ＋2.0‰, which indicates that the sulfur might originate from magma or possibly erupted directly from volcano or was leached from ore-hosted volcanic rock. The lead from ores in most deposits displays radioactive genesis character （206pb/204pb〉18.140, 207Pb/204pb〉15.584, 208pb/204pb〉38.569） and lead isotope values of ores are higher than those of wall rocks, which indicates that the lead was likely leached from the ore-hosted volcanic rocks. Based on isotope data, two significant Pb-Zn metallogenesis are delineated, which are Mid- and Late-Proterozoic sedimentary exhalative metailogenesis （The single zircon U-Pb, Sm-Nd isochronal and Ar-Ar dating ages of ore- hosted wall rocks are calculated to be among 933-1788 Ma.） and Yanshanian magmatic hydrothermal superimposed and alternated metallogenesis （intrusive SHRIMP zircon U-Pb and Rb-Sr isochronal ages between 127-154 Ma）.

Microstructure and electrochemical characteristics of nonstoichiometric La-rich AB_5-type alloy for Ni/MH battery electrode

The nonstoichiometric La-rich mischmetal (designated by MI)-based hydrogen storage alloy with a composition of MI(Ni0.64Co0.2Mn0.12Al0.04)(4.76) was prepared by arc melting and annealed at 1173 K for 10 h to investigate the effect of annealing treatment on the microstructure and electrochemical characteristics of the alloy. X-ray diffraction analysis showed that annealing can cause a release of the crystal lattice strain and an increase in amounts of the La2Ni7-type second phase in MI(Ni0.64Co0.20Mn0.12Al0.04)(4.76) alloy. Scanning electron microscopy and electron probe microanalysis examinations indicated that annealing leads to disappearance of the dendrite structure in the as-cast alloy, growth of crystal grain, and decrease of composition segregation. The annealing at 1173 K for 10 h flattened and extended the potential plateau and increased the maximum discharge capacity to 328 mA center dot h/g from 310 mA center dot h/g and the cycling life. The mechanism of the improvement in electrochemical characteristics was discussed based on the alloy microstructure change induced by annealing.